Note: Descriptions are shown in the official language in which they were submitted.
CA 02540560 2006-03-28
WO 2005/035934
PCT/US2004/023007
SOLID-LIQUID SEPARATION OF OIL-BASED MUDS
FIELD OF THE INVENTION
The invention is directed to a method of solid-liquid separation of oil-based
muds.
In particular, the invention relates to a method of separating solid and
liquid phases of oil-
based muds by contacting the muds with a water-in-oil emulsion comprising a
polymer
derived from at least one water-soluble monomer.
BACKGROUND OF THE INVENTION
Oil-based muds form a general class of materials that minimally comprise a
mixture of particulate solids in an oil-continuous phase. A subset of oil-
based muds is oil-
based drilling muds, which contain functional fluids used to improve drilling
operations in
several ways. These fluids are circulated through and around the drill bit to
lubricate and
cool the bit, provide flotation to help support the weight of the drill pipe
and casing, coat
the wellbore surface to prevent caving in and undesirable fluid flow, and to
carry drill
cuttings away from the bit to the surface. Such oil-based drilling fluids are
oil-continuous
compositions that may also contain an aqueous solution (e.g. calcium chloride
brine) as a
discontinuous phase (making the fluids water-in-oil inverse emulsions),
emulsifiers to
stabilize the inverse emulsion, rheology modifying agents (e.g. oleophilic
clays), weighting
agents (e.g. barium sulfate), fluid loss control agents (e.g. lignins), and
other additives
(e.g. lime). Used oil-based drilling muds will contain, in addition to the
above components,
drill cuttings and other dissolved or dispersed materials derived from the
drilled medium or
from other sources of contamination such as process and environmental waters.
Waste
oil-based muds are simply used or contaminated oil-based drilling muds
containing a
sufficient concentration of drill cuttings or other components to warrant
either a disposal or
a recycling of the mud.
Waste management of oil-based drilling muds, made with either diesel or
synthetic
oil, is a high priority for companies drilling both onshore and offshore
wells. The current
trend in managing these waste oil-based drilling muds (i.e. drilling fluids
laden with
cuttings) is moving towards reclamation and recycling of the muds. Much of
this trend is a
response to regulation. Reclamation and recycle of these fluids almost always
requires a
good separation of the oil phase and possibly the aqueous phase from the oil-
based
drilling muds.
1
CA 02540560 2006-03-28
WO 2005/035934 PCT/US2004/023007
The methods used for solid-liquid separation of oil-based drilling muds
(OBDMs),
have included mechanical, thermal and some chemical treatments. The chemical
treatments include the use of: sodium silicates in U.S. Patent No. 2,476,846;
organic
solvents in U.S. Patent Application No. 4,040,866; a neutralization-
flocculation scheme in
which a dissolved polymeric flocculant was employed in U.S. Patent No. US
4,482,459;
polyethylene oxides to dewater OBDMs (Sharma, S. K. and A. G. Smelley (1991)
"Use of
flocculants in dewatering of drilling muds." Advances in Filtration and
Separation
Technology 3 (Pollution Control Technol. Oil Gas Drill. Prod. Oper.) pp 43-
51); water and
surfactants or oil washes in U.S. Patent No. US 5,090,498; carboxylic acids in
combination with pH cycling in U.S. Patent No. 5,156,686; supercritical fluid
extraction
(Eldridge, R. B. (1996) "Oil Contaminant Removal from Drill Cuttings by
Supercritical
Extraction." Industrial & Engineering Chemistry Research 35(6): 1901-1905);
surfactants
with pH adjusters in U.S. Patent Application Publication No. 2003056987 Al,
and acid
treatment followed by a dissolved water-soluble polymer in U.S. Patent
Application
Publication No. 2003083532 Al.
In a thesis by Julio Oswaldo Bello Torres and Luis Hernando Perez Cardenas
entitled "Analisis TecnicoEconomico de un Metodo FisicoQuimico Alternativo
Para la
Separacion de Agua y Solidos en Lodos Base Aceite", Fundacion Universidad de
America, Santafe De Bogota, D.C. (1999), both solid and water-in-oil emulsion
polymer
flocculants were diluted in water at about 3% by weight concentration and then
mixed with
OBDMs. None of the polymer flocculants were directly or neatly mixed with
OBDMs prior
to dilution with water.
While the above treatments may be used to some extent in the separation of
particulate solids from OBDMs, they each have their own drawbacks, whether it
be in
terms of process inefficiency, the generation of additional volumes of waste
to be treated,
or lack of economic viability.
The inventors of the present invention have discovered that the direct use of
neat
or oil-diluted water-in-oil emulsions in which the discrete phase contains a
polymer
comprising at least one water-soluble monomer provides excellent separation of
oil from
oil-based drilling muds. This is rather surprising since there are some
documents that
have statements that indicate a lack of utility of water-soluble polymers in
treating OBDMs
(e.g., Field, S. D., A. Wojtanowicz, et al. (1987) "Deliquification of
oilfield drilling slurries
and production sludges." Proceedings of the Industrial Waste Conference, 41st:
pp 481-
7).
2
CA 02540560 2006-03-28
WO 2005/035934
PCT/US2004/023007
SUMMARY OF THE INVENTION
This invention relates to a method of achieving a solid-liquid separation of
an oil-
based mud comprising the step of contacting said oil-based mud with a water-in-
oil
emulsion comprising a polymer derived from at least one water-soluble monomer,
where
the polymer is not dissolved prior to contact with the oil-based mud, mixing
the water-in-oil
emulsion and the oil-based mud and separating the solid phase from the liquid
phase in
the oil-based mud.
In addition, this invention also relates to a composition comprising an oil-
based
mud with a water-in-oil emulsion comprising a polymer derived from at least
one water-
soluble monomer, wherein the polymer is not dissolved prior to contact with
the oil-based
mud.
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, "Drill cuttings" means earth-based solids including,
but
not limited to gravel, sand, dirt, soil, mud, minerals, fragmented rock, clay,
silt and ash.
"Oil" means a hydrocarbon based material such as natural or synthetic oils,
fats,
greases, or waxes, including but not limited to those derived from animal,
vegetable, or
mineral sources; synthetic oils and greases containing hydrocarbon groups,
such as
organopolysiloxanes (silicones); and mixtures thereof. The oil typically
comprises a
substantially hydrocarbonaceous oil or grease, usually a natural or synthetic
petroleum or
petroleum product, such as crude oil, heating oil, bunker oil, kerosene,
diesel, gasoline,
paraffin blends, internal olefins, C16 to C18 alkene blends, naphtha, shale
oil, coal oil, tar,
lubricating oil, motor oil, solvents, waxes, and lubricating greases.
Additionally, the oil may
contain small amounts of a finely divided discontinuous phase in the form of
aqueous
droplets, solid particles, or a mixture of both.
"Mud" means a flowable mixture of finely divided solids in a liquid.
"Oil-Based Mud" (0BM) means a mud containing at least some oil (e.g., at least
1% or at least 2% or at least 5% oil by volume based on the total volume of
the mud.
"Oil-based drilling mud" (OBDM) means oil-based mud that is used in the
drilling
industry comprising drilling muds and drill cuttings. Typical oil-based
drilling muds
comprise an oil-continuous phase and may also contain an aqueous solution
(e.g.
sodium, potassium or calcium chloride brine) as a discontinuous phase along
with other
additives such as emulsifiers, rheology modifying agents (e.g. oleophilic
clays), weighting
agents (e.g. barium sulfate), fluid loss control agents (e.g. lignins), etc.
Further
3
CA 02540560 2012-08-09
78521-28
description of such drilling muds may be found in U.S. Patent Application
Publication
Nos. 2003/0056987 Al and 2003/0083532 Al, as well as U.S. Patent No.
5,156,686.
-"Water-in-oil emulsion" means a dispersion of an aqueous phase as discrete
droplets or particles within a continuous oil phase. The composition of the
discrete
aqueous phase may consist of a water-containing material that may range from
substantially water, to a concentrated aqueous solution of a low-molecular
weight water-
soluble substance, to a concentrated aqueous solution of a water-soluble or
water-
swellable polymer, or any combination thereof. The continuous oil phase may
also
contain oil-soluble substances.
"Well dispersed" means contacting or mixing components until a homogeneous or
substantially homogeneous composition ensues.
This invention relates to a method of separating a solid phase from a liquid
phase
in an oil-based mud comprising the steps of contacting the oil-based mud with
a water-in-
oil emulsion comprising a polymer derived from at least one water-soluble
monomer,
where the polymer is not dissolved prior to contact with the oil-based mud;
mixing the
-water-in-oil emulsion and the oil-based mud and separating the solid phase
from the liquid
phase. The liquid phase may be an oil phase and/or an aqueous phase.
Preferably, the
liquid phase is an oil phase. In the case where the liquid phase contains both
oil and
water, this invention also relates to a method of separating the oil and
aqueous-phases
both from each other and from the solid phase. Therefore, separating the solid
phase from
the liquid phase also may mean separating the oil and aqueous phases both from
each
other and from the solid phase.
This invention also contemplates separating a solid phase from a liquid phase
in
an oil-based drilling mud.
= The inventors have discovered that degree of separation of a solid phase
from a
liquid phase in the oil-based mud (OBM) is greatly improved if the polymer in
the water-in-
oil emulsion is not substantially solubilized or dissolved prior to contact
with the OBM.
The polymer in the water-in-oil emulsion, which may be cationic, anionic,
ampholytic, or nonionic, is derived from at least one water-soluble monomer.
The water-
soluble monomer is typically a water-soluble vinyl monomer. Non-limiting
examples of
water-soluble monomers that may be used include cationic, anionic or non-ionic
monomers such as (alkyl)acrylamide, (alkyl)acrylic acid, N-vinylpyrrolidone, N-
vinylacetamide, N-vinylformamide, acrylonitrile, furmaric acid, crotonic acid,
maleic acid,
hydroxyalkyl methacrylates, 2-acrylamido-2-alkylsulfonic acids wherein the
alkyl group
4
CA 02540560 2006-03-28
WO 2005/035934
PCT/US2004/023007
contains 1 to 6 carbon atoms, styrene sulfonic acids, vinyl sulfonic acids;
and salts of any
of the foregoing thereof; or monomers having the structure of formulas I, ll
or III
71 ? R2
CH2= C ¨ C¨ X¨A¨N:õ
R4
Formula I
Ri 0 R2
I I I
R3 Z -
I
R4
Formula II
Ri
I
CH2=-C¨CH2 z R2
\ _
N+ Z
CH2=C¨ C I-1/2 \
I R4
R5
Formula III
wherein R1, R2, and R5 are each independently hydrogen or a C1 to Cg alkyl; R3
and R4
are each independently hydrogen, a C1 to C12 alkyl, aryl, arylalkyl, or
hydroxyethyl; and R2
and R4 or R2 and R3 can combine to form a cyclic ring containing one or more
hetero
atoms; Z is the conjugated base of an acid, X is oxygen or ¨NR6 wherein R6 is
hydrogen
or a C1 to C6 alkyl; and A is a C1 to C12 alkylene.
In one embodiment, the water-soluble vinyl monomers are (alkyl)acrylamide,
(alkyl)acrylic acid and its salts and vinyl sulfonic acid.
The term (alkyl)acrylamide means an acrylamide monomer or alkylacrylamide
monomers such as methacrylamide, ethylacrylamide, butylacrylamide and the
like.
Likewise, (alkyl)acrylic acid means acrylic acid, methacrylic acid,
ethylacrylic acid and the
like. The term "(meth)acrylamide" means acrylamide or methacrylamide.
As mentioned above, the polymer in the water-in-oil emulsion may be derived
from
more than one monomer (e.g., a copolymer, terpolyrner, etc.). In the present
invention,
5
CA 02540560 2006-03-28
WO 2005/035934 PCT/US2004/023007
the term "copolymer' means a polymer derived from two or more monomers. A
"homopolymer means a polymer derived from just one monomer. The term "polymer"
means either a homopolymer or copolymer. An ampholytic polymer contains both
anionic
and cationic monomers in the same chain, not necessarily in equal molar
amounts.
In one embodiment, the polymer in the water-in-oil emulsion is a copolymer of
an
(alkyl)acrylamide monomer and at least one second monomer selected from N-
vinylpyrrolidone, N-vinylacetamide, N-vinylformamide, acrylonitrile, acrylic
acid,
methacrylic acid, ethylacrylic acid, furmaric acid, crotonic acid, maleic
acid, hydroxyalkyl
methacrylates, 2-acrylamido-2-alkylsulfonic acids wherein the alkyl group
contains 1 to 6
carbon atoms, styrene sulfonic acids; and salts of any of the foregoing
thereof; or
monomers of Formulas I, II or III. Preferably the (alkyl)acrylamide is a
(meth)acrylamide
and more preferably acrylamide.
In another embodiment, the polymer in the water-in-oil emulsion is a cationic
copolymer of (meth)acrylamide and at least one second monomer selected from
the
group consisting of N,N-dimethylaminoethyl(meth)acrylate or its salts,
quaternary N,N-
dimethylaminoethyl(meth)acrylates, including the methylchloride or
methosulfate salts,
tertiary or quaternary N,N-dimethylaminopropyl acrylamides, tertiary or
quaternary N,N-
dimethylaminomethyl acrylamides and diallyl dimethyl ammonium halides.
In another embodiment, the polymer in the water-in-oil emulsion is an anionic
copolymer of (meth)acrylamide and at least one second monomer selected from
acrylic
acid, methacrylic acid, ethylacrylic acid, furmaric acid, crotonic acid,
maleic acid,
hydroxyalkyl methacrylates, 2-acrylamido-2-alkylsulfonic acids where the alkyl
group
contains 1 to 6 carbon atoms, styrene sulfonic acids; or salts of any of the
foregoing
thereof.
In another embodiment, the polymer in the water-in-oil emulsion is an anionic
copolymer of (meth)acrylamide and (meth)acrylic acid.
In another embodiment, the polymer in the water-in-oil emulsion is a
homopolymer
or copolymer of monomers selected from (meth)acrylamide, monomers of Formula I
and II
and combinations thereof, where R1 is hydrogen or methyl, R2 to R4 are methyl
or ethyl, A
is C1 to C4 alkylene and X is defined above.
In another embodiment, the polymer in the water-in-oil emulsion is an
ampholytic
polymer.
In another embodiment, the water-in-oil emulsion is a mixture of water-in-oil
emulsions containing different polymers of the types described herein.
The water-in-oil emulsion used to separate the oil from the OBM comprise a
continuous oil phase, which generally includes a water-immiscible inert
organic liquid and
6
CA 02540560 2012-08-09
78521-28
a surfactant or surfactant mixture, and a discontinuous phase, preferably
aqueous, which
is in the form of droplets or particles containing the polymer derived from a
water soluble
monomer described above. The ratio of the aqueous phase to the oil phase
should be
about 0.1:1 to about 10:1, or about 0.20:1 to about 8:1, or about 0.5:1 to
about 3:1.
Preferably, the water-in-oil emulsion comprises from about 1 to about 80%
weight percent
aqueous phase, based on the total weight of the water-in-oil emulsion. The
amount of
polymer contained within the discontinuous phase of the water-in-oil emulsions
can
generally range from about a few percent, (e.g., about 2% or about 5% or about
10%) up
to about 70% or about 8.0% or about 90% or even about 100% by weight, based on
the
total weight of discontinuous aqueous phase. The discontinuous aqueous phase
may,
therefore, contain 100% polymer and 0% water and are prepared using known
methods in
the art.
'The total concentration of the polymer in the water-in-oil emulsion is about
1%, or
about 5%, or about 10%, or about 20%, or about 40% by weight, on the lower
range to
about 50%, or about 60% or about 70% by weight on the higher range, based on
the total
weight of the emulsion.
The polymers employed in the water-in-oil emulsions of the present invention
are
formed by conventional emulsion or suspension polymerization of the water-
soluble
monomers or mixtures of monomers disclosed above. , Examples of such
polymerizations
are those disclosed in U.S.. Patent. Nos. 5,037,881; 5,037,553; 4,651,912;
4,521,317;
4,439,332; 5,548,020; 5,945, 494; 5,763,523 and European Patent Application EP
0 374
457 AZ .
Emulsion polymerization procedures involve the preparation of two= phases. The
aqueous phase comprises the water-soluble monomer(s), and optionally branching
agent
and chain-transfer agent dissolved in water, and other additives well known to
those
skilled in this art, suchas stabilizers and pH adjusters. The oil phase
comprises a water-
insoluble oil phase such as hydrocarbon solution of surfactant(s). The aqueous
'phase and
oil phase are mixed and homogenized in a conventional apparatus until the
average
discrete phase particle.size is less than about 10 microns and a suitable bulk
viscosity is
obtained. The emulsion is then transferred to a suitable flask wherein the
emulsion is
agitated and sparged with nitrogen for about thirty minutes. A polymerization
initiator,
such as sodium metabisulfite solution, is then continuously added to the
solution to begin
polymerization. Polymerization is allowed to exotherm to the desired
temperature which is
maintained by cooling until cooling is no longer required. Finished emulsion
product is
cooled to 25'C.
7
CA 02540560 2006-03-28
WO 2005/035934
PCT/US2004/023007
Typical surfactants useful in the oil phase of the emulsion include anionic,
cationic
and nonionic surfactants. Preferred surfactants include polyoxyethylene
sorbitol fatty
acids, sorbitan sesquioleate, polyoxyethylene sorbitan trioleate, sorbitan
monooleate,
polyoxyethylene (20) sorbitan monooleate, sodium dioctylsulfosuccinate,
oleamidopropyldimethyl amine, sodium isosteary1-2-lactate, polyoxyethylene
sorbitol
monooleate or mixtures thereof and the like. Emulsifiers and surfactants
useful in the
invention are well documented in the relevant literature, for example, the
Atlas HLB
Surfactant Selector which is commonly referred to by those in this field.
Most known free-radical initiators may be employed to initiate polymerization.
Suitable for use are azobisisobutyronitrile; oxygen with sodium sulfite,
and/or sodium
metabisulfite; 2,2,-azobis(2-methyl-2-amidinopropane)dihydrochloride; ammonium
persulfate and ferrous ammonium sulfate hexahydrate, or other redox pairs.
Organic
peroxides may also be employed for polymerizing ethylenically unsaturated
monomers.
Particularly useful for the purpose of this invention is t-butyl
hydroperoxide, see Modern
Plastics Encyclopedia/88, McGraw Hill, October 1987, pp. 165-8. The amount of
the
initiator that is typically used in emulsion polymerization is about 1 to 1000
ppm, or about
to 750 ppm, or about 50 to 500 ppm, based on the amount of monomer present.
The temperature used for emulsion polymerization is typically about 10 C to
about
90 C, or about 20 C to about 75 C, or about 25 to 60 C.
20 If a branched polymer is desirable, the polymerization of the
monomers is
conducted in the presence of a polyfunctional branching agent to form the
branched
homopolymer or copolymer. The polyfunctional branching agent comprises
compounds
having either at least two double bonds, a double bond and a reactive group or
two
reactive groups. Polyfunctional branching agents should have at least some
water-
25 solubility. Illustrative of those compounds containing at least two
double bonds are
methylenebisacrylamide; methylenebismethacrylamide; polyethyleneglycol
diacrylate;
polyethyleneglycol dimethacrylate; N-vinyl acrylamide; divinylbenzene;
triallylammonium
salts; N-methylallylacrylamide; and the like. Polyfunctional branching agents
containing at
least one double bond and at least one reactive group include glycidyl
acrylate; acrolein;
methylolacrylamide; and the like. Polyfunctional branching agents containing
at least two
reactive groups include aldehydes, such as glyoxal; diepoxy compounds and
epichlorohydrin and the like.
Branching agents should be used in sufficient quantities to assure a highly
branched copolymer product. Preferably, a branching agent content of from
about 4 to
about 80 molar parts per million, based on initial monomer content, is added
to induce
sufficient branching of the polymer chain.
8
CA 02540560 2006-03-28
WO 2005/035934
PCT/US2004/023007
A chain transfer agent may also be used in the emulsion polymerization. A
molecular weight modifying or chain-transfer agent is used to control the
structure and
solubility of the polymer. Highly branched, polymer products are obtained when
a chain-
transfer agent is used, in optimum concentration, in conjunction with the
branching agent.
Many such chain-transfer agents are well known to those skilled in the art.
These include
alcohols, such as isopropyl alcohol; mercaptans; thioacids; phosphites and
sulfites and
sodium hypophosphite, although many different chain-transfer agents may be
employed.
In the absence of a chain-transfer agent, the incorporation of even extremely
small
amounts of branching agent, e.g. 5 parts per million may cause crosslinking. A
crosslinked polymer may also be used in this invention. That is, the polymer
within the
discrete droplets may actually be water-swellable and not water-soluble, or it
may
comprise a mixture of water-swellable and water-soluble species, and still act
in an
efficacious manner in the solid-liquid separation process described herein for
oil-based
muds. The term "branched polymers" includes compositions that consist of
mixtures of
polymers with different degrees of branching, including linear, within the
same sample.
The term "crosslinked polymers" include compositions that consist of mixtures
of polymers
with different degrees of crosslinking and branching, including linear, within
the same
sample.
A subset of emulsion polymerization is inversion microemulsion polymerization,
which typically has more surfactants in the oil phase than emulsion
polymerization. It is
produced by (i) preparing a monomer containing microemulsion by mixing an
aqueous
solution of monomers with a hydrocarbon liquid containing an appropriate
amount of
surfactant or surfactant mixture to form an inverse microemulsion comprising
small
aqueous droplets dispersed in a continuous oil phase and (ii) subjecting the
monomer-
containing microemulsion to polymerization conditions. If desirable to form
small aqueous
droplets, mixing energy, e.g., shear, may be applied to the emulsion to obtain
smaller
aqueous droplets.
The formation of the inverse microemulsion depends on the proper selection of
surfactant concentration and the hydrophilic-lypophylic balance (HLB) of the
surfactant or
surfactant mixture. Temperature, nature of the oil phase and composition of
the aqueous
phase will also affect microemulsion formation.
The one or more surfactants selected should provide an HLB value ranging from
about 6 to about 12. The required HLB may vary from this, depending on the
nature of the
monomers, the nature and proportion of comonomer (if any) and the nature of
the oil
phase. In addition to the appropriate HLB range, the surfactant concentration
must be
sufficient to form an inverse microemulsion. Too low surfactant concentrations
will not
0
CA 02540560 2006-03-28
WO 2005/035934 PCT/US2004/023007
result in the formation of a microemulsion, while excessively high
concentrations will
increase costs without imparting significant benefit. For example, the minimum
amount of
surfactant for forming an inverse microemulsion containing anionic polymer
will vary
depending on the HLB of the surfactant system used; such minimum surfactant
amount,
based on total weight, is depicted by the hachured portion within the curve
representing
surfactant concentration verses HLB value in the sole Figure in U.S. Patent
No.
4,681,912, see the Figure and column 3 lines 22-37 therein.
The selection of the organic phase has a substantial effect on the minimum
surfactant concentration necessary to obtain the inverse microemulsion and
typically
contains an oil such as hydrocarbons or hydrocarbon mixtures. Isoparafinic or
linear
hydrocarbons or mixtures thereof are most desirable in order to obtain
inexpensive
formulations.
Polymerization of the microemulsion may be carried out in any manner known to
those skilled in the art. Initiation may be effected with a variety of thermal
and redox free
radical initiators, including peroxides, e.g. t-butyl hydroperoxide; azo
compounds, e.g.
azobisisobutyronitrile; inorganic compounds, such as potassium persulfate and
redox
couples, such as ferrous ammonium sulfate/ammonium persulfate. Initiator
addition may
be effected any time prior to the actual polymerization per se. Polymerization
may also be
effected by photochemical irradiation processes, such as ultraviolet
irradiation or by
ionizing irradiation from a cobalt 60 source.
Typically the aqueous solution which contains the monomers and optional
comonomers as defined above and any conventional additive such as, but not
limited to,
chelating agents such as ethylenediaminetetraacetic acid, difunctional
monomers such as
methylene bis(acrylamide), pH adjusters, initiators and the like are added to
a pre-mixed
solution of the oil and surfactant. Once the aqueous and oil solutions are
combined, an
inverse microemulsion forms, typically without the need for shearing
Anionic polymers may be formed by emulsion polymerization of anionic monomers
such as those listed above. Another method to form an anionic polymer is by at
least
partially hydrolyzing a non-ionic acrylamide polymer by the addition of a
caustic hydrolysis
agents (i.e., so as to convert at least a portion of the amide groups on the
polymer to
carboxylate groups), which results in the formation of a partially hydrolyzed
anionic
acrylamide polymer. Hydrolysis agents useful in the present invention include,
but are not
limited to, alkali metal hydroxides and quaternary ammonium hydroxides. The
preferred
hydrolysis agents, however, are the alkali metal hydroxides and, more
particularly,
sodium, potassium, and lithium hydroxides. In fact, however, any material
which will
provide an alkali solution may be used as a hydrolysis agent.
CA 02540560 2006-03-28
WO 2005/035934 PCT/US2004/023007
The hydrolysis agent should be added to the polymeric emulsion as an aqueous
solution slowly and with mixing. The most preferred hydrolysis agent is a 10
to 50%
aqueous solution of alkali metal hydroxide, with a 20 to 40% solution being
more preferred
and a solution of about 30% being most preferred. The concentration of the
solution of the
alkali metal hydroxide is within the range of 0.2 to 30%, preferably 4 to 12%,
by weight
based on the polymeric emulsion. The percentage of hydrolysis agent used will
vary
however, according to the degree of hydrolysis desired.
While solutions with the above concentrations of the alkali metal hydroxides
are,
as noted above particularly useful, it is important to note that higher or
lower
concentrations of alkali metal hydroxides in aqueous media may also be used.
Conditions
favoring the use of lower concentrations of the hydrolysis agent include the
desire for low
levels of hydrolysis and stability factors. Higher concentrations may be used
when a
substantial degree of hydrolysis is desired without excessive dilution. As
would be
understood by one skilled in the art, stability considerations also play a
role in this
determination.
The hydrolysis reaction may be conducted at room temperature but more
favorable results are obtained at elevated temperatures. Generally the
reaction may be
performed within the range of from about 100 to about 70 C. The preferred
temperature
range for this reaction is, however, from about 35 to about 55 C. The length
of time
required for the hydrolysis reaction depends upon the reactants, their
concentrations, the
reaction conditions and the degree of hydrolysis desired.
The molecular weight of the polymer in the water-in-oil emulsion is not
critical and
may range from about as low as 1000 to as high as a crosslinked polymer.
Preferably,
the number average molecular weight of the polymer can range from as low as
1000, or
about 5000 or about 10000, or about 100000, to as high as about infinite
(crosslinked) or
about 60 million, or about as high as 40 million for a water soluble polymer.
In one embodiment of the present invention, the water-in-oil emulsions may be
pre-dispersed in oil prior to contact with the OBM. If the emulsions are pre-
dispersed with
oil, the concentration of the polymer in the predisposed water-in-oil emulsion
is about
0.01% to about 20%, or about 0.1% to about 10% by weight based on the total
weight of
the emulsion. Any type of oil may be suitable for the pre-dispersion.
Preferred types of oil
for pre-dispersion include kerosene, diesel, paraffin blends, internal olefins
or C16-C18
alkene blends. A more preferred oil is whatever oil is used in the OBM.
As mentioned previously, the water-in-oil emulsion containing the above-
mentioned polymers is contacted with the OBM in order to separate the solids
from the
liquids in the OBM. The inventors have surprisingly discovered that degree of
separation
11
CA 02540560 2006-03-28
WO 2005/035934 PCT/US2004/023007
of solids from the liquids in the OBM is greatly improved if the polymer in
the water-in-oil
emulsion is not substantially solubilized or dissolved (e.g., contacted or
dissolved in
excess water) prior to contact with the OBM (e.g., see Examples 7 to 9 below).
The method of the present invention may further comprise the addition of a
surfactant and/or water. The surfactant may be added to the OBM before, during
or after
the addition of the water-in-oil emulsion. Preferably, the surfactant is added
to the OBM
subsequent to the addition of the water-in-oil emulsion. The surfactant may be
any surface
active agent that changes the interfacial tension between the oil phase and
the aqueous
phase in the OBM. Preferred surfactants are high HLB surfactants with an HLB
value
greater than about 10 or a value of about 10 to about 40 or about 10 to about
30 or about
10 to about 20. Also preferred are anionic surfactants or high HLB anionic
surfactants
with an HLB greater than about 10 or about 10 to about 40 or about 10 to about
30 or
about 10 to about 20.
Examples of classes of such surfactants that may be used are sulfosuccinates,
sulfosuccinamates, alkylaryl sulfonates, diphenylsulfonates, benzene sulfonic
acids,
(alkyl)naphthalene sulfonic acids, sulfates and sulfonates of oils and fatty
acids, sulfates of
ethoxylated alkyl phenols, sulfates of alcohols, sulfates of ethoxylated
alcohols, petroleum
sulfonates, sulfates of fatty esters, sulfonates of condensed naphthalenes,
aliphatic or
aromatic phosphate esters, alkoxylated alcohols, sodium paraffin sulfonates
and mixtures
thereof.
Examples of such surfactants that may be used are sodium
diisobutylsulfosuccinate, sodium diamylsulfosuccinate, sodium
dicyclohexylsulfosuccinate,
sodium dioctylsulfosuccinate, sodium bis(2-ethylhexyl)sulfosuccinate,
tetrasodium N-(1,2-
dicarboxy-ethyl)-N-octadecylsulfosuccinamate, disodi urn ethoxylated alcohol
half-ester
sulfoscuccinate, sodium di(1,3-dimethylbutyl)sulfosuccinate, sodium
bistridecylsulfosuccinate and mixtures thereof.
The amount of water-in oil emulsion to be contacted with the OBM should be
about 0.1%, or about 0.5% by weight on the lower range to about 20%, or about
10%, or
about 5%, or about 2% by weight on the upper range, based on the total weight
of the
ODMB. The preferred range of the amount of water-in oil emulsion to be
contacted with
the OBM is 0.5% to 5% by weight.
The OBM and water-in-oil emulsion is preferably mixed. Any suitable method may
be used to mix the components. Non-limiting examples of methods or apparatus
that may
be used to mix the components are flow mixers, in-line mixers, gas agitation
or
mechanical mixers. More detailed information on these mixing techniques or
apparatus
may be found, for example, in Chemical Engineer's Handbook, Fifth Edition,
McGraw-Hill
12
CA 02540560 2006-03-28
WO 2005/035934 PCT/US2004/023007
Book Company, 1973, pp 19-3 to 19-14 and 21-3 to 21-10. Preferably the OBM and
the
water-in-oil emulsion composition are mixed such that it is well-dispersed.
The oil may be separated from the OBM by mechanical or gravitational
separation.
Non-limiting examples of mechanical separation is the use of a centrifuge,
cyclone,
pressure filtration or vacuum assisted filtration. Example of gravitational
separation is the
use of a clarifier, thickener or continuous countercurrent decantation. More
detailed
information on such means may be found, for example, in Chemical Engineer's
Handbook, Fifth Edition, McGraw-Hill Book Company, 1973, pp 19-44 to 19-104
and 21-
11 to 21-14.
Another embodiment of this invention is a composition comprising an oil-based
mud with a water-in-oil emulsion comprising a polymer derived from at least
one water-
soluble monomer, wherein the polymer is not dissolved prior to contact with
the oil-based
mud. The same polymers as mentioned above may be used in the composition. The
composition may further comprise a surfactant. The same surfactants listed
above may
be used in the composition. Preferably, the water-in-oil emulsion is first
added to the
OBM prior to the addition of the surfactant.
The present invention will now be illustrated by the following examples. The
examples are not intended to limit the scope of the present invention. In
conjunction with
the general and detailed descriptions above, the examples provide further
understanding
of the present invention.
EXAMPLES
EXAMPLE 1 to 6. Oil Separation of OBDM's using a Water-in-oil Emulsion.
Three different waste OBDMs were obtained from a waste drilling mud treatment
facility in Colombia. The oil in these muds was a diesel-type oil. The mud
properties are
tabulated below.
Table 1. Waste Oil-Based Drilling Muds from Colombia.
OBDM Description Mud BSW Retort analysis
Electrical
(ppb) (96) _ (V)
_
OBDM A Blend of aged OBDMs 9.75 44 32 / 12 / 56 157
from 2rld and 3rd perforation
stages.
OBDM B Blend of aged OBDMs 9.80 44 28 / 16 / 56 - 160
from 2nd and 3rd perforation
stages.
13
CA 02540560 2012-08-09
=
78521-28
OBDM C Fresh, high solids OBDM 8/0 48 40 / 8 / 52
240
with coarse solids removed
by centrifugation.
The compositions of the OBDMs were determined using two methods. A retort
analysis resulted in a determination of the individual amounts of water,
solids and oil. The
combined (water + solids) contents of the OBDMs both before and after
treatment were
also determined using a solvent extraction method, designated as the BSW (base
solids
and water ratio) method, and described below.
A 40 ml sample of the OBDMD oil phase is sampled after gravity settling.
Approximately 40 ml of Varsol (aliphatic hydrocarbonfluid from ExxonMobil)
and 3 drops
of demulsifier surfactant was added to the OBDM and mixed. The resulting
Composition
mixture was centrifuged for 2 Minutes at 2000 rpm. The volume % of solids
separated
after centrifugation was determined and Multiplied by 2 to obtain the BSW
value.
The BSW value is the volume percentage of solids and water that centrifuges
out
from a sample after it has been diluted 1:1 with an aliphatic hydrocarbon oil
(e:g. Varsol).
Treatments resulting in separated oil phases that yield BSW values less than
or equal to
about 2% are considered to have been successful treatments.
=
Experimental Protocol
The experimental protocol that was used to assess the efficacy of a solid-
liquid
separation treatment of an OBDM is as follows. The waste oil-based drilling
mud sample
is mixed using an overhead stirrer in order to provide a well dispersed
homogeneous
composition. A sample of the mud is weighed into a 600-ml glass beaker. The
water-in-oil
emulsion (Polymer Emulsion.' described below) is dispersed into diesel Oil in
a separate
beaker using a spatula until the composition is homogeneous. The water-in-oil
is then =
added to the mud and mixed for 3 minutes using an overhead stirrer until the
composition
is homogeneous. The treated Mud is allowed to settle for 1 hour and
observations are
then made on the physical state of the treated mud. The gravity-separated
liquid phase is
decanted and analyzed using the BSW method.
Polymeric Emulsion I is an inverse water-in-oil emulsion in which the discrete
aqueous phase contains a copolymer of acrylamide (45 mol%) and
acryloyloxyethyltrimethylammonium chloride (55 mol%), with 10 ppm of 1\1,N'-
methylenebisacrylamide as branching agent, prepared in a manner similar to
U.S. Patent
No. 5,945,494 (example 3B). When this polymeric
emulsion is pre-dispersed into diesel oil, it disperses well and forms a
homogeneous
composition.
14
CA 02540560 2012-08-09
78521-28
The results of various mud treatments using Polymeric Emulsion I are described
in
Table 2.
Table 2. Treatment of OBOMs A, B, and C with Polymeric Emulsion 1.
Ex. OBDM OBDM Poly. Poly. Disp. oil Disp. BSW
Observations
(g) Emul. Emul. oil (ml) (%)
(m1)
1 A 150 None 0 None 0 44 Control
2 B 150 None 0 None 0 44 Control
3 C 150 None 0 None 0 48 Control
4 A 150 I t5 Diesel 150 1.8 Large flocs
visible, good oil
separation
5 B 150 I 1.5 Diesel 150 1.25 Large flocs
visible, good oil
separation
6 C 150 I 1.5 Diesel 150 2.0 - MediUm flocs,
good oil
separation
The results of various mud treatments using Polymeric resulted in the
formation of
large aggregates that separated readily under the action of gravity, leaving
an easily
recoverable, clean oil phase.
EXAMPLES 7 to 9. Pre-dissolving the Water-in-oil Emulsion in Water before
Contacting with the OBDM
These examples illustrate that if the polymeric emulsion is pre-dissolved in
water,
so as to form an aqueous polymer solution, then the solid-liquid separation of
the treated
0E3DM is-poor. - -
Polymeric Emulsion Ills an inverse polymeric emulsion in which the discrete
aqueous phase contains a copolymer of acrylamide (45 mol%) and 2-
acryloyloxyethyltrimethylammonium chloride (55 mol%) prepared in a manner
similar to
U.S. Patent No. 5,763,523 (example 19).
Polymeric Emulsions I and II were separately dissolved in water by mixing 1 ml
of
= the polymeric emulsion into 100 ml of tap water using a Braun mixer for
15 seconds,
followed by quiescent aging for 1 hour. This resulted in a homogenous aqueous
polymer
solution.
The OBDM used in these tests was OBDM B used in Examples 2 and 5 above.
CA 02540560 2006-03-28
WO 2005/035934 PCT/US2004/023007
Experimental Protocol
The experimental protocol used to assess the efficacy of a solid-liquid
separation
treatment is as follows. The waste oil-based drilling mud sample is mixed
using an
overhead stirrer in order to provide a homogeneous composition. A sample of
the mud is
weighed into a 250-ml glass beaker. Either the polymer emulsion is dispersed
into diesel
oil in a separate beaker using a spatula until the composition is homogeneous,
or the
polymeric emulsion is dissolved in water as described above. The dispersed
polymeric
emulsion or dissolved polymer solution is then added to the mud and mixed in
for 30
seconds using an overhead stirrer at 200 rpm. Observations are then made on
the
physical state of the treated mud. About 100 ml of the treated mud is loaded
into a glass
centrifuge tube and centrifuged for 10 minutes at 2000 rpm. Observations are
made on
the physical state of the centrifuged mud. Note is taken of the volume of each
layer, and
its general physical character (e.g. compacted solids, slurry, water,
emulsion, oil).
The results of various mud treatments using Polymeric Emulsions I and II are
described in Table 3 below.
Table 3. Treatment of OBDM B with Polymeric Emulsions I and II.
Ex. OBDM Poly. Poly. Disp.. Disp. Sep. Sep. Sep. Observations
B Emul. Emul. Liquid liquid phase phase phase
(9) (ml) (ml) (vol A) quality
7 60 1 0.6 Diesel 50 Oil 73
Clean oil Clear cut
separation of
Solids 27 phases.
8 100 I 1.0 Water 100 Slurry# 80 Poor Polymer
solution did
not mix
Solids 20 well
with
OBDM.
9 100 II 1.0 Water 100 Slurr{ 98 Poor
Polymer
solution did
not mix
Solids 2 well
with
OBDM.
* Dispersing liquid or solvent
Unseparated oil-based mud with high solids content
The results demonstrate a clean separation of aggregated solids and a clean
oil
phase occurred when OBDM B was treated with Polymeric Emulsion I dispersed in
diesel
oil (Example 7). However, when Polymeric Emulsions I or II were pre-dissolved
in water,
the resulting aqueous polymer solutions did not mix well with the OBDM B, and
the
16
CA 02540560 2006-03-28
WO 2005/035934
PCT/US2004/023007
separation of the oil from the solids phase was very poor or non-existent
(Examples 8 and
9).
EXAMPLES 10 to 15. Oil Separation Usina Combination of Water-in-oil Emulsions,
Surfactant and Water in the OBDM.
This set of examples demonstrates the utility of treatments for the separation
of oil
from OBDMs based on combinations of polymeric inverse emulsions, surfactants
and
water.
The OBDM was obtained from a waste drilling mud treatment facility in Mexico
and
is designated OBDM D. The oil in this mud a diesel-type oil. The mud
properties are
tabulated below (Table 4). The solids fall into two categories: high gravity
solids (HGS)
and low gravity solids (LGS).
Table 4. Waste Oil-Based Drilling Mud from Mexico.
OBDM Description Mud
Oil Water solids HGS LGS
name
weight (wt %) (wt %) (vol %) (wt %) (wt %)
(PPb)
OBDM D Waste diesel-based 12.79 40 36.0
24.0 12.58 10.73
drilling mud.
Experimental Protocol
The experimental protocol used to assess the efficacy of a solid-liquid
separation
treatment is as follows. The oil-based drilling mud sample is mixed in order
to provide a
homogeneous composition. A 60-gram sample of the mud is weighed into a 250-ml
plastic beaker. Water is added, if appropriate, and mixed in by hand using a
spatula until
the composition is homogeneous. Surfactant is added, if appropriate, and mixed
in by
hand using a spatula until the composition is homogeneous. The polymer
emulsion is
dispersed into an oil compatible with the OBDM in a separate plastic beaker,
and mixed in
by hand using a spatula until the composition is homogeneous. Polymeric
Emulsion I,
described above, is then added to the partially treated mud, if appropriate,
and mixed in
by hand using a spatula until the composition is homogeneous. In some cases
the
undispersed polymeric emulsion is added directly to the mud, and then mixed in
by hand
using a spatula until the composition is homogeneous. Observations are then
made on
the physical state of the treated mud. About 50 ml of the treated mud is
loaded into a
plastic centrifuge tube and centrifuged for 10 minutes at 2000 rpm (e.g. in an
IEC Centra
GP-8 swinging basket centrifuge). Observations are made on the physical state
of the
17
CA 02540560 2006-03-28
WO 2005/035934
PCT/US2004/023007
centrifuged mud. Note is taken of the volume of each layer, and its general
physical
character (e.g. compacted solids, slurry, water, emulsion, oil).
The general appearances of the separated phases and the results of various mud
treatments using Polymeric Emulsion I are described in Table 5.
Table 5. Treatment of OBDM D with Polymeric Emulsion I
Ex. OBDM Poly. Poly. Disp. oil Disp. oil Water Surf. 1 Sep.* Sep.
Observations
(g) Emul. Emul. (ml) (ml) (m1)
phase phase
(ml) (vol %)
60 1 1.5 Diesel 5 15 3 Oil 19 Clear cut
separation of
phases, clean
oil.
Water 24 Transparent
water layer.
Solids 57 Compacted
solids layer
11 60 1 1.5 Diesel 5 0 3 Slurry 100 No
separation.
Water 0
Solids 0
12 60 1 1.5 Diesel 5 15 0 Oil 10 Dirty
oil layer.
Slurry 90 Unseparated
mud
Solids 0
13 60 1 1.5 None 0 15 3 Oil 14 Clear cut
separation of
phases, clean
oil.
Water 19 Transparent
water layer
Solids 67 Compacted
solids layer
14 60 None 0 Diesel 5 15 3 Slurry 100 No
separation.
Water 0
Solids 0
60 1 1.5 Diesel 5 15 3 Oil 21 Clear cut
separation of
phases, clean
oil.
Water 21 Transparent
water layer
Solids 58 Compacted
solids layer
* Surfactant was a mixture of a dioctylsulfosuccinate (27 wt%) and a
dicarboxyethyl
octadecylsulfosuccinamate (57 wt%) in 2-propanol (16 wt%).
10 *Key to appearance of separated phase
Oil = reasonably clean oil layer
Water = a reasonably clean water layer.
Emulsion = a poorly clarified water layer or 'rag' layer
18
CA 02540560 2006-03-28
WO 2005/035934
PCT/US2004/023007
Slurry = a mud phase with lower solids than the original, but not completely
separated
Solids = a well separated layer of solids, possibly containing imbibed water
Examples 10 to 15 show that, for the specific OBDM D, using all three
components (polymer emulsion, surfactant and water) in the treatment program
resulted
in the best separation of oil phase from the solids. In some cases not only
were solids
separated from the liquid phase, but the liquid phase was additionally
separated into oil
and aqueous phases. It was also clear, from this group of examples, that the
water-in-oil
emulsion was a necessary component in any efficacious treatment.
EXAMPLES 16 to 20. Treatment of OBDM Using Various Water-in-oil Emulsions
This set of examples demonstrates the range of polymeric emulsion types that
may be used in successfully treating OBDMs to produce a solid-liquid
separation.
Polymeric Emulsion III is an inverse polymeric emulsion in which the discrete
aqueous phase contains a copolymer of acrylamide (45 mol%) and
dimethylaminoethylmethacrylate (55 molc/o) prepared as follows. The oil phase
and
aqueous phase described below are first prepared separately.
Oil Phase Preparation: In a 1000 mL resin flask is place 8.64g sorbitan
monooleate, 12.15g ethoxylated alcohol (60% E0) and 167.71g low odor paraffin
oil. The
mixture is stirred with a magnetic stirrer until it was homogeneous.
Aqueous Phase Preparation: To a 1000 mL beaker is added 145.29 g aqueous
acrylamide (52% solution), 160.50g deionized water, 204.45 g
dimethylaminoethyl
methacrylate, and 1.40 g Versenex 80 (a product of Dow Chemical Company).
Cooling
is provided to maintain the temperature below 100 F. Approximately 70g of
concentrated
H2SO4 is slowly added to adjust the pH to 3.5. To the mixture are added 0.028
g
hypophosphite, and enough deionized water to bring the total aqueous phase to
594 g.
The mixture is stirred with a magnetic stirrer until it was homogeneous.
Thereafter the oil and aqueous phases are combined and homogenized to yield a
monomer emulsion. The polymerization initiator, 0.14g Vazo0 64 (a product of
DuPont
Chemical Company), was then added to the monomer emulsion. The monomer
emulsion
is purged with nitrogen and heated to 125 to130 F to start the polymerization.
The
emulsion temperature is maintained at 125 to 130 F until the polymerization is
complete.
The emulsion is cooled to room temperature and 8.0 g ethoxylated alcohol (60%
E0) is
added with stirring.
19
CA 02540560 2012-08-09
78521-28
Polymeric Emulsion IV is an inverse polymeric emulsion in which the discrete
aqueous phase contains a copolymer of acrylamide (90 mol%) and
methacrylamidopropyltrimethyl-ammonium chloride (10 mol%) is prepared in a
manner
similar to European patent application EP 0 374 457 A2 (example 16).
Polymeric Emulsion V is an inverse polymeric emulsion in which the discrete
aqueous phase contains a copolymer of acrylamide (70 mol%) and ammonium
acrylate
(30 mol%) prepared in a manner similar to U.S. Patent No. 5,763,523 (example
23).
Polymeric Emulsion VI is an inverse polymeric emulsion in which the discrete
aqueous phase contains a.copolymer of acrylamide (90 mol%) and sodium acrylate
(10
mol%) made from the alkaline hydrolysis of an inverse polymeric emulsion in
which the
discrete aqueous phase contains poly(acrylamide). This is prepared in a manner
similar to
U.S. Patent No. 5,548,020 (example 5) .
The OBDM was obtained from a waste drilling mud treatment facility in Mexico,
and is designated OBDM E. The oil in this mud was a diesel-type oil. The mud
properties
are shown in Table 6 below. The solids fall into two categories: high gravity
solids (HGS)
and low gravity solids (LGS).
Table 6. Waste Oil-Based Drilling Mud from Mexico.
OBDM Description Mud weight -Oil
Water solidi HGS LGS (wt
name (ppb) (wt %) (wt %-) (vol %)- -(wt
%) %)
oppm Waste diesel-based 14.61 40 26.5 33.5
16.71 16.11
E 'drilling Mud.
The results of The various treatments of the polymeric emulsion with OBDM E
are
shown in Table 7.
Table 7. Treatment of OBDM D with Polymeric Emulsions III - VI
- Exp. OBDM E Poly. Poly. Disp. Disp oil Water ,Surf. Sep. Sep.
Observations
(g). Emul. Emul oil (m1) (m1) (m1)
phase phase
(m1) . (vol %)
16 60 III 1.5 Diesel 5 0 0 Oil 12 Clear cut
separation of
phases, clean
oil.
Water 28 Transparent
water layer.
Solids 60 Compacted
-
solids layer.
17 60 IV 1.5 Diesel 5 15 3 - Oil 22 Clear cut
separation of
CA 02540560 2006-03-28
WO 2005/035934 PCT/US2004/023007
phases, clean
oil.
Water 27 Turbid, white
water layer.
Solids 51 Compacted
solids layer
18 60 V 1.5 Diesel 5 15 3 Oil 17 Clear cut
separation of
phases, clean
oil.
Water 21 Turbid water
layer.
Solids 62 Moderately
compacted
solids layer.
19 60 VI 1.5 Diesel 5 15 3 Oil 12 Clear
cut
separation of
phases, clean
oil.
Water 33 Transparent
water layer
Solids 55 Moderately
compacted
solids layer.
Water 31 Transparent
water layer
Solids 52 Compacted
solids layer.
Surfactant was a mixture of a dioctylsulfosuccinate (27 wt%) and a
dicarboxyethyl
octadecylsulfosuccinamate (57 wt%) in 2-propanol (16 wt%).
*Water and surfactant were pre-mixed before adding to the OBDM.
These examples show that either cationic or anionic polymeric emulsions may be
successfully used to separate the different phases in OBDMs. Example 16 also
shows
that separation of the oil and aqueous phases can result from using only the
polymeric
emulsion in the treatment, without the addition of a surfactant.
EXAMPLES 21 to 23. Treatment of Various Oil Type OBDMs
This set of examples demonstrates that the invention may be used to produce a
solid-liquid separation in OBDMs consisting of different oil types. Previous
Examples 1-20
were based on diesel-type oil OBDMs. The other major class of oils used to
produce
OBDMs is synthetic oils, which includes paraffins and olefins. A waste
synthetic OBDM
was prepared by adding low gravity solids to a typical synthetic OBDM based on
an olefin
21
CA 02540560 2006-03-28
WO 2005/035934
PCT/US2004/023007
oil. The original synthetic oil-based mud is designated OBDM F, and the waste
synthetic
oil-based mud is designated OBDM G. The mud properties are shown in Table 8
below.
Table 8. Waste Synthetic Oil-Based Drilling Mud.
OBDM Description
Mud Oil Water solids HGS LGS
name weight (wt %) (wt %) (vol %) (wt %) (wt %)
(PPb)
OBDM F Synthetic oil-based 13.16 54.0 21.5 24.5
18.14 5.45
drilling mud.
OBDM G Synthetic oil-based
15.0
drilling mud with
added LGS.
Polymeric Emulsion VII is an inverse polymeric emulsion in which the discrete
aqueous phase contains a copolymer of acrylamide (45 mol%) and 2-
acryloyloxyethyltrimethylammonium chloride (55 mol%), with 17 ppm of N,N'-
methylenebisacrylamide as branching agent, prepared in a manner similar to
U.S. Patent
No. 5,945,494 (example 3B). When this polymeric emulsion is mixed into diesel
oil, it
disperses well and forms a homogeneous composition.
The results of various treatments are shown in Table 9.
Table 9. Treatment of OBDM G with Polymeric Emulsions III and VII
Ex. OBDM Poly. Poly. Disp. Disp. Water Surf. Sep. Sep.
Observations
(m1) (vol %)
21 60 VII 1.5 Diesel 5 15 3 Oil 16 Clear
cut
separation of
phases,
brown oil.
Water 16 Transparent
water layer.
Solids 68 Compacted
solids layer.
22 60 III 1.5 Diesel 5 15 3 Oil 18 Clear
cut
separation of
phases,
brown oil.
Solids 82 Moderately
compacted
solids layer.
23 60 III 1.5 None 0 15 3 Oil 17 Clear
cut
separation of
phases,
brown oil.
Solids 62 Moderately
compacted
solids layer.
22
CA 02540560 2006-03-28
WO 2005/035934
PCT/US2004/023007
Good separation of the solid and liquid phases was achieved using two
different
polymeric emulsions (Examples 21 and 22). Example 23 shows that in some cases
the
polymeric emulsion does not need to be pre-dispersed into oil, and may be used
neat.
EXAMPLES 24 to 29. Treatment OBDMs Using Polymeric Emulsions and Various
Surfactants
This set of examples illustrates that combinations of polymeric emulsion and
surfactant can be chosen to selectively create either an oil-solids
separation, or an oil-
water-solids separation in an OBDM.
The OBDM was obtained from a drilling mud treatment facility in the United
States,
and is designated OBDM H. The oil in this mud was a synthetic-type oil. The
mud
properties are shown in Table 10 below. The solids fall into two categories:
high gravity
solids (HGS) and low gravity solids (LGS).
Table 10. Waste Oil-Based Drilling Mud from the United States.
OBDM Description Mud weight Oil
Water solids HGS LGS (wt
name (ppb) (wt
%) (wt %) (vol %) (wt %) %)
OBDM Synthetic-oil based 13.43 58 17.5 24.5 20.8 2.7
H drilling mud.
The results of the various treatments of OBDM H with polymeric emulsion Ill
and
surfactants are shown in Table 11. Only the surface active agent in the
surfactant
composition is indicated.
Table 11. Treatment of OBDM H with Polymeric Emulsion Ill and Various
Surfactants
Exp. OBDM Poly. Poly. Disp. Disp Surface Active Surf. Sep. Sep.
Observations
H Emul Emul oil oil agent (ml) phase phase
(9) (ml) (ml) (vol %).
solids of solids in oil.
slurry
Solids 40 Compacted
solids layer.
81 Ill 3 olefin 3 Na 2 Oil- 70 Very dirty
slurry
dicarboxyethyl solids of
solids in oil.
octadecylsulfo slurry
succinamate
Solids 30 Compacted
solids layer.
26 81 III 3 olefin 3 Na 2 Oil 40
Clear cut
dicyclohexyl
separation of
sulfosuccinate phases,
slightly
_ dirty oil.
Solids 60 Compacted
solids layer.
23
CA 02540560 2006-03-28
WO 2005/035934 PCT/US2004/023007
27 81 III 2 olefin 2 Na diamyl 3 Oil 35 Clear
cut
sulfosuccinate
separation of
phases, slightly
dirty oil.
Water 18
Clear water
layer.
Solids 47 Compacted
solids layer.
28 80 None 0 None 0 Na 2 Oil 62 Dirty oil.
dicarboxyethyl
octadecylsulfo
succinamate
= Solids 38 Compacted
solids layer.
29 80 none 0 none 0 Na 2 Oil 51 Dirty oil.
dicyclohexyl
sulfosuccinate
Water 6
Slightly dirty
water
Solids 43 Compacted
solids layer.
30 80 none 0 none 0 Na diamyl 2 Oil 46 Dirty
oil.
sulfosuccinate
Water 15
Slightly dirty
water
Solids 39 Compacted
solids layer.
The above examples show that only particular combinations of polymeric
emulsion
and surfactant resulted in useful solid-liquid separations, and that the OBM
can be
selectively separated into either oil-and-solids, or oil-water-solids phases,
depending on
the particular combination of polymeric emulsion and surfactant. The use of
surfactant
alone, while it did allow some improvement in the separation, always resulted
in a dirty oil
phase (solids contamination). The use of polymeric emulsion in combination
with certain
surfactants allowed for both the improved separation and a cleaner recovered
oil phase.
Our experience shows that different combinations of polymeric emulsion and
surfactant
may be required to effectively treat (i.e. cause a useful solid-liquid
separation) different
OBMs, depending on the mud compositions.
The invention described and claimed herein is not to be limited in scope by
the
specific embodiments herein disclosed, since these embodiments are intended as
illustrations of several aspects of the invention. Any equivalent embodiments
are
intended to be within the scope of this invention. Indeed, various
modifications of the
invention in addition to those shown and described herein will become apparent
to those
skilled in the art from the foregoing description. Such modifications are also
intended to
fall within the scope of the appended claims.
24
